KR100497938B1 - Method for producing complex oxide powder and complex oxide powder - Google Patents
Method for producing complex oxide powder and complex oxide powder Download PDFInfo
- Publication number
- KR100497938B1 KR100497938B1 KR10-2002-0085002A KR20020085002A KR100497938B1 KR 100497938 B1 KR100497938 B1 KR 100497938B1 KR 20020085002 A KR20020085002 A KR 20020085002A KR 100497938 B1 KR100497938 B1 KR 100497938B1
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- South Korea
- Prior art keywords
- oxide powder
- batio
- reaction
- producing
- composite oxide
- Prior art date
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- 239000000843 powder Substances 0.000 title claims abstract description 139
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 53
- 239000002131 composite material Substances 0.000 claims abstract description 51
- 238000001354 calcination Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims description 78
- 238000000034 method Methods 0.000 claims description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 31
- 239000013078 crystal Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 24
- 238000004090 dissolution Methods 0.000 claims description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- -1 hydroxide anhydride Chemical class 0.000 claims description 14
- 239000011882 ultra-fine particle Substances 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 230000001678 irradiating effect Effects 0.000 claims description 5
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical group O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical class [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910010413 TiO 2 Inorganic materials 0.000 abstract description 52
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 abstract description 10
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 abstract description 6
- 229910002113 barium titanate Inorganic materials 0.000 abstract description 6
- 239000010419 fine particle Substances 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 41
- 239000000243 solution Substances 0.000 description 38
- 238000003786 synthesis reaction Methods 0.000 description 30
- 239000000047 product Substances 0.000 description 24
- 239000002245 particle Substances 0.000 description 21
- 229910052719 titanium Inorganic materials 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000002441 X-ray diffraction Methods 0.000 description 18
- 229910052788 barium Inorganic materials 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 13
- 230000005856 abnormality Effects 0.000 description 12
- 239000002002 slurry Substances 0.000 description 11
- 150000004703 alkoxides Chemical class 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003609 titanium compounds Chemical class 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- JMGZEFIQIZZSBH-UHFFFAOYSA-N Bioquercetin Natural products CC1OC(OCC(O)C2OC(OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5)C(O)C2O)C(O)C(O)C1O JMGZEFIQIZZSBH-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- IVTMALDHFAHOGL-UHFFFAOYSA-N eriodictyol 7-O-rutinoside Natural products OC1C(O)C(O)C(C)OC1OCC1C(O)C(O)C(O)C(OC=2C=C3C(C(C(O)=C(O3)C=3C=C(O)C(O)=CC=3)=O)=C(O)C=2)O1 IVTMALDHFAHOGL-UHFFFAOYSA-N 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- FDRQPMVGJOQVTL-UHFFFAOYSA-N quercetin rutinoside Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 FDRQPMVGJOQVTL-UHFFFAOYSA-N 0.000 description 2
- IKGXIBQEEMLURG-BKUODXTLSA-N rutin Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](C)O[C@@H]1OC[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](OC=2C(C3=C(O)C=C(O)C=C3OC=2C=2C=C(O)C(O)=CC=2)=O)O1 IKGXIBQEEMLURG-BKUODXTLSA-N 0.000 description 2
- ALABRVAAKCSLSC-UHFFFAOYSA-N rutin Natural products CC1OC(OCC2OC(O)C(O)C(O)C2O)C(O)C(O)C1OC3=C(Oc4cc(O)cc(O)c4C3=O)c5ccc(O)c(O)c5 ALABRVAAKCSLSC-UHFFFAOYSA-N 0.000 description 2
- 235000005493 rutin Nutrition 0.000 description 2
- 229960004555 rutoside Drugs 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000004689 octahydrates Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
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- C01G23/04—Oxides; Hydroxides
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
- C04B35/62805—Oxide ceramics
- C04B35/62818—Refractory metal oxides
- C04B35/62821—Titanium oxide
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
- C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
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Abstract
본 발명은 미립이고 결정성이 우수한 고품질의 티탄산 바륨 등의 복합 산화물을 저렴하게 제조할 수 있는 복합 산화물 분말의 제조 방법 및 복합 산화물 분말을 제공하는 것을 목적으로 한다.An object of the present invention is to provide a method for producing a composite oxide powder and a composite oxide powder which can produce a composite oxide such as barium titanate of high quality and excellent crystallinity at low cost.
본 발명에 따르면, Ba(OH)2·8H2O를 가열하여 Ba용해액을 생성하고, 250m2 /g 이상의 비표면적을 갖는 TiO2분말과 상기 Ba용해액을 반응시켜서 결정성이 우수한 입방정(立方晶) BaTiO3를 제조하고, 이러한 입방정 BaTiO3를 하소하여 미립이고 결정성이 우수한 정방정(正方晶) BaTiO3를 제조한다.According to the present invention, Ba (OH) 2 · 8H 2 O is heated to form a Ba solution, and the TiO 2 powder having a specific surface area of 250 m 2 / g or more is reacted with the Ba solution to provide excellent crystallinity.立方晶) produce a BaTiO 3, and a fine particle by calcining such a cubic BaTiO 3 to produce an excellent crystallinity tetragonal (正方晶) BaTiO 3.
Description
본 발명은 복합 산화물 분말의 제조 방법 및 복합 산화물 분말에 관한 것으로, 보다 상세하게는 유전체 세라믹스 등의 전자 재료에 사용되는 복합 산화물 분말의 제조 방법 및 상기 제조 방법을 사용하여 제조된 복합 산화물 분말에 관한 것이다.The present invention relates to a method for producing a composite oxide powder and a composite oxide powder, and more particularly, to a method for producing a composite oxide powder used in an electronic material such as dielectric ceramics, and a composite oxide powder produced using the manufacturing method. will be.
근래에 들어 적층 커패시터의 소형 대용량화의 발전에 따라, 유전체 소자의 박층화가 진행되고 있다. 이러한 종류의 박층화된 적층 커패시터를 제조하기 위해서는, 유전체 세라믹스의 결정 입자를 작게 하고 입자 성장을 억제해야 해야 하는데, 이를 위해서는 세라믹 원료인 복합 산화물이 미립이고 결정성이 높은 것이 요구된다.In recent years, with the development of miniaturization of a multilayer capacitor, the thickness of a dielectric element is progressing. In order to manufacture this kind of thin-layered multilayer capacitors, it is necessary to reduce the crystal grains of the dielectric ceramics and to suppress the growth of particles, which requires that the composite oxide, which is a ceramic raw material, is fine and has high crystallinity.
그리고, 이러한 종류의 복합 산화물의 대표적인 것으로서, 티탄산 바륨(BaTiO3) 분말이 알려져 있는데, 이러한 BaTiO3분말의 제조 방법으로는 종래부터 습식 합성법이라 불리는 방법이 알려져 있다(구보테루 이치로, 가토우 마사노리, 후지타 다카시, '티탄산 바륨(BaTiO3)의 습식 합성법', 사단법인 일본화학회, 공업 화학 잡지 71권 1호(1968), p.114-118 참조).As a representative example of this kind of composite oxide, a barium titanate (BaTiO 3 ) powder is known, and a method called a wet synthesis method is known in the art as a method of producing such BaTiO 3 powder (Kiboteru Ichiro, Kato Masanori, Fujita Takashi, `` Wet Synthesis of Barium Titanate (BaTiO 3 ) '', Japanese Chemical Society, Japan Chemical Society, Vol. 71, No. 1 (1968), p. 114-118).
상기 문헌에서는 우선, 수산화 바륨 8수화물(Ba(OH)2·8H2O)과 95%정도의 물을 포함한 겔형상의 산화 티탄(TiO2)을, 탄산 가스를 차단하고 기계적으로 마쇄·혼합하여 양자를 반응시킨 후, 반응 생성물 안의 침전을 분리한다. 이어서, 이것에 아세트산(6N)을 첨가하여 50℃로 가열하고, 이것에 의해 미반응의 Ba(OH)2와 부차적으로 생성되는 BaCO3 및 Ba2TiO4를 용해 추출하고, 침전물을 수세·건조하여 BaTiO3를 얻고 있다.In this document, first, a gel-like titanium oxide (TiO 2 ) containing barium hydroxide octahydrate (Ba (OH) 2 .8H 2 O) and about 95% water is mechanically ground and mixed by blocking carbon dioxide gas. After reacting both, the precipitate in the reaction product is separated. Then, acetic acid (6N) was added thereto and heated to 50 ℃ and dissolved extract BaCO 3, and Ba 2 TiO 4 is secondary generated and Ba (OH) 2 of the unreacted Thereby, washed with water and the precipitate and drying. BaTiO 3 is obtained.
또한, 다른 종래 기술로는 티탄 화합물의 가수 분해 생성물과 수용성 바륨염을 강알칼리 수용액 안에서 반응시켜서 BaTiO3미립자를 제조하는 가수 분해법이 제안되어 있다(일본 특허공고 평 3-39014호 공보 참조).As another conventional technique, a hydrolysis method for producing BaTiO 3 fine particles by reacting a hydrolysis product of a titanium compound with a water-soluble barium salt in a strong alkaline aqueous solution has been proposed (see Japanese Patent Application Laid-open No. 3-39014).
상기 공보에서는 TiCl4 등의 티탄 화합물을 가수 분해하여 얻어진 가수 분해 생성물과 Ba(NO3)2를, 수소 이온 지수(pH)가 13.0이상인 KOH나 NaOH 등의 강알칼리 수용액 안에서 반응시키고, 이것에 의해 입방정 BaTiO3를 얻고 있다.In the above publication, a hydrolysis product obtained by hydrolyzing a titanium compound such as TiCl 4 and Ba (NO 3 ) 2 are reacted in a strong alkali aqueous solution such as KOH or NaOH having a hydrogen ion index (pH) of 13.0 or higher, thereby allowing cubic crystals. BaTiO 3 is obtained.
또한, 그 외의 BaTiO3분말의 제조 방법으로는, 종래부터 분쇄법, 수열 합성법, 졸-겔법, 알콕시드 수산화물법(Alkoxide-Hydroxide Route)이 알려져 있다.Further, the other manufacturing method of the BaTiO 3 powder, from the conventional grinding method, hydrothermal synthesis method, sol-gel method, alkoxide method hydroxide (Alkoxide-Hydroxide Route) is known.
분쇄법은, 저렴하게 미립 원료를 얻는데 적절한 방법이며, BaCO3와 TiO2의 혼합 슬러리를 볼밀(ball mill)이나 샌드밀(sand mill) 등의 분쇄기로 기계적으로 분쇄하여 미립화, 균일화한 후, 건조·하소하여 BaTiO3를 얻는다.The pulverization method is an appropriate method for obtaining finely divided raw materials, and the mixed slurry of BaCO 3 and TiO 2 is mechanically pulverized by using a ball mill or a sand mill to atomize and homogenize, and then dried. Calcination to obtain BaTiO 3 .
수열 합성법은, 예를 들면 티탄원으로서 비표면적이 크고 활성이며 많은 OH기를 함유한 함수산화(含水酸化) 티탄([Ti(OH)6]2-)을 미리 TiCl4나 Ti알콕시드의 가수 분해를 통하여 제조하고, 상기 함수산화 티탄을 Ba(OH)2와 함께 오토클레이브(auto clave) 안에서 가열함으로써 고온 고압 하로 하고, Ba2+의 TiO2 안으로의 확산을 촉진하여 BaTiO3를 합성한다.Hydrothermal synthesis is, for example, hydrolysis of TiCl 4 or Ti alkoxide in advance of hydrous titanium ([Ti (OH) 6 ] 2- ), which has a large specific surface area and is active as a titanium source and contains many OH groups. It is prepared through, and the hydrous titanium oxide is heated under high temperature and high pressure by heating in an autoclave with Ba (OH) 2 to promote diffusion of Ba 2+ into TiO 2 to synthesize BaTiO 3 .
졸-겔법은, 티탄 화합물과 바륨 화합물을 직접 반응시키는 방법으로, 티탄 알콕시드와 바륨 알콕시드의 혼합 용액으로부터 출발하는 방법, 또는 1분자 내에서 티탄과 바륨을 화학양론비로 갖는 알콕시드 전구체 용액으로부터 출발하는 방법이 알려져 있다.The sol-gel method is a method of directly reacting a titanium compound and a barium compound, starting from a mixed solution of titanium alkoxide and barium alkoxide, or from an alkoxide precursor solution having titanium and barium in stoichiometric ratio in one molecule. How to start is known.
알콕시드 수산화물법은, 티탄원으로서 티탄 알콕시드를 사용하고, 상기 티탄 알콕시드를 Ba2+용액 안에서 가수 분해시켜서, BaTiO3를 제조하고 있다. 즉, 티탄 알콕시드를 Ba(OH)2용액 안에서 가수 분해시킨 경우, 반응 개시 시에는 알콕시드 용액이 곧 백탁(白濁)하기 때문에, Ba(OH)2용액 안에서, 우선 TiO2(또는 [Ti(OH) 6]2-)를 형성하고, 그 후 Ba2+와의 반응에 의해 BaTiO3를 생성하는 방법이며, 수열 합성법과 마찬가지로 Ba2+를 TiO2안으로 확산시킴으로써 BaTiO3가 생성된다.In the alkoxide hydroxide method, titanium alkoxide is used as a titanium source, and the titanium alkoxide is hydrolyzed in a Ba 2+ solution to produce BaTiO 3 . That is, when titanium alkoxide is hydrolyzed in Ba (OH) 2 solution, since the alkoxide solution soon becomes cloudy at the start of the reaction, in the Ba (OH) 2 solution, TiO 2 (or [Ti ( forming OH) 6] 2-), and then a method of generating a BaTiO 3 by reaction of Ba 2+, the BaTiO 3 is generated as with hydrothermal synthesis method by spreading the Ba 2+ in TiO 2.
그러나, 상기 문헌에서는 미반응의 Ba(OH)2와 침전 생성물을 분리할 필요가 있고, 게다가 부생성물로서 생성된 BaCO3나 Ba2TiO4를 용해 추출하여 BaTiO 3와 분리해야 하며, 생산 공정이 번잡하고, 또한 부생성물로서 Ba2TiO4를 포함할 가능성이 있기 때문에, BaTiO3는 결정으로서 불완전하다고 생각된다.However, in this document, it is necessary to separate the unreacted Ba (OH) 2 from the precipitate product, and furthermore, it is necessary to dissolve and extract BaCO 3 or Ba 2 TiO 4 produced as a by-product to separate from BaTiO 3. It is thought that BaTiO 3 is incomplete as a crystal because it is complicated and may contain Ba 2 TiO 4 as a by-product.
더욱이 95%의 수분을 함유한 TiO2를 사용하고 있기 때문에, TiO2의 농도가 낮고, 이 때문에 Ba(OH)2와의 합성 반응이 촉진되기 어려운 문제점이 있다.Furthermore, since TiO 2 containing 95% of water is used, the concentration of TiO 2 is low, which causes a problem that the synthesis reaction with Ba (OH) 2 is difficult to be promoted.
또한, 상기 문헌에서는 아세트산과 같은 산성 용액에서 용해 처리를 실시하기 때문에, 결정이 손상을 입거나, 혹은 Ba2+가 용출하여 BaTiO3의 구성 몰비가 변동할 우려가 있다.Further, in the above document, since the dissolution treatment is carried out in an acidic solution such as acetic acid, there is a fear that the crystals are damaged or Ba 2+ elutes, so that the molar ratio of the constituents of BaTiO 3 may fluctuate.
또한, 상기 공보에서는 수소 이온 지수(pH)가 13.0이상인 강알칼리 수용액 안에서 티탄 화합물의 가수 분해 생성물과 수용성 바륨염을 반응시키고 있기 때문에, K나 Na 등의 알칼리 금속이 BaTiO3에 고착될 우려가 있다. 이 때문에, BaTiO3의 생성 후에 세정 처리를 실시하여도 불순물이 수백 ppm정도 잔류하고, 이러한 불순물이 절연 저항값 등의 불량 원인이 되기 때문에, 박층화가 진행된 현재의 유전체 세라믹스 원료로는 부적당하다.In the above publication, since a hydrolysis product of a titanium compound is reacted with a water-soluble barium salt in a strong alkaline aqueous solution having a hydrogen ion index (pH) of 13.0 or more, alkali metals such as K and Na may adhere to BaTiO 3 . For this reason, even after the cleaning process is performed after the formation of BaTiO 3 , impurities remain about several hundred ppm, and such impurities cause defects such as an insulation resistance value, and thus are not suitable as the current dielectric ceramic raw material in which thinning has been advanced.
또한, 상기 분쇄법에서는 볼밀 등에 포함된 지르코니아 등의 분쇄 매체가 제품인 BaTiO3 안에 혼입될 우려가 있어서, 고순도의 BaTiO3분말을 얻는 것이 곤란하다. 게다가, 이 분쇄법에서는 비교적 큰 입자 직경을 갖는 BaCO3나 TiO2를 마쇄하고 있기 때문에, 미립화에도 한계가 있다. 즉, 입도 분포도 넓어져서 입자 성장이 불균일해지며, 이 때문에 세라믹스 입자의 입자 직경을 원하는 미립 또한 균일하게 하는 것이 곤란하다는 문제점이 있다.Further, in the grinding method, there is a possibility that grinding media such as zirconia contained in a ball mill or the like may be mixed into BaTiO 3 , which is a product, and it is difficult to obtain BaTiO 3 powder having high purity. In addition, in this grinding method, since BaCO 3 and TiO 2 having a relatively large particle diameter are ground, there is a limit to atomization. In other words, the particle size distribution is also widened and the grain growth becomes non-uniform, and thus there is a problem that it is difficult to make the desired particle size of the ceramic particles uniform.
또한, 상기 수열 합성법에서는 대규모의 장치가 필요하며, 또한 제조 공정도 배치(batch) 처리가 되기 때문에, 작업성이나 생산 효율이 악화되고, 비용 저하에도 한계가 있으며, 고가의 것이 된다.In addition, in the hydrothermal synthesis method, a large-scale apparatus is required, and the manufacturing process is also subjected to a batch treatment, so that workability and production efficiency are deteriorated, and there is a limit to cost reduction and is expensive.
또한, 상기 졸-겔법에서는 약 400℃에서 하소함으로써 입방정 BaTiO3를 얻을 수 있으나, 바륨 알콕시드는 대기중의 수분과 격렬하게 반응하여 발연(發煙)해 버리기 때문에, 건조 분위기에서 실시해야 하고, 또한 출발 원료인 알콕시드류는 고가라는 문제점이 있다.In addition, in the sol-gel method, cubic BaTiO 3 can be obtained by calcining at about 400 ° C. However, barium alkoxide reacts violently with moisture in the air and thus fumes, and therefore, should be carried out in a dry atmosphere. Alkoxides that are starting materials have a problem of being expensive.
또한, 상기 알콕시드 수산화물법은 티탄 알콕시드를 Ba(OH)2 안에 용해시켜서 티탄산 바륨의 합성 반응을 수행하고 있는데, 이러한 합성 반응을 완결시키기 위해서는 과잉의 Ba(OH)2를 필요로 하거나, 혹은 알칼리원으로서 NaOH나 KOH를 첨가할 필요가 있다.In addition, the alkoxide hydroxide method dissolves titanium alkoxide in Ba (OH) 2 to carry out a synthesis reaction of barium titanate, and in order to complete such a synthesis reaction, an excessive amount of Ba (OH) 2 is required, or It is necessary to add NaOH or KOH as the alkali source.
따라서, 과잉의 Ba(OH)2를 사용한 경우에는, 상기 합성 반응 후에도 용액 안에 Ba2+가 잔존하고, 이 때문에 BaTiO3의 조성 제어가 곤란해지며, 게다가 바륨의 회수 설비가 필요하게 된다.Therefore, when excess Ba (OH) 2 is used, Ba 2+ remains in the solution even after the above-described synthesis reaction, which makes it difficult to control the composition of BaTiO 3 , and further requires a recovery facility for barium.
또한, NaOH나 KOH를 첨가한 경우에도, 상기 합성 반응 후의 용액 안에 Na+나 K+가 잔존하기 때문에, BaTiO3 안에 불순물로서 Na나 K가 혼입되어 고순도의 BaTiO 3를 얻을 수 없다.In addition, even when the addition of NaOH or KOH, because the Na + or K + remaining in the solution after the synthesis reaction, BaTiO 3 is Na or K is mixed as an impurity it can not be obtained in a highly pure BaTiO 3.
게다가, 알콕시드의 가수 분해에 따라 생성된 알콜은 유기 용매이며, 위험물에 해당하기 때문에 방폭(防爆) 설비가 필요하게 되어, 비용이 높아지는 것을 초래하는 문제점이 있다.In addition, the alcohol produced by the hydrolysis of the alkoxide is an organic solvent, and since it corresponds to a dangerous substance, an explosion-proof facility is required, resulting in a high cost.
본 발명은 이러한 점을 감안하여 이루어진 것으로, 미립이고 결정성이 우수한 고품질의 티탄산 바륨 등의 복합 산화물을 저렴하게 제조할 수 있는 복합 산화물 분말의 제조 방법 및 복합 산화물 분말을 제공하는 것을 목적으로 한다.This invention is made | formed in view of this point, Comprising: It aims at providing the manufacturing method of composite oxide powder which can manufacture high quality composite oxide, such as barium titanate excellent in crystallinity, and a composite oxide powder at low cost.
본 발명자들은 간단한 방법으로 미립이고 결정성이 우수한 티탄산 바륨 분말을 얻기 위해 심도깊게 연구한 결과, 결정수를 함유한 수산화 바륨 8수화물(Ba(OH)2·8H2O)을 가열하여 용해시킴으로써, 반응 활성이고 고농도인 바륨 용해액을 생성할 수 있고, 또한 상기 용해액과 산화 티탄(TiO2) 분말을 반응시킴으로써, 고순도의 미립자 BaTiO3분말을 용이하게 제조할 수 있다는 것을 발견하였다. 더욱이 이러한 발견은 BaTiO3와 유사한 복합 산화물에 적용을 확대할 수 있다고 생각된다.The present inventors have studied in depth to obtain a fine and excellent crystallinity of barium titanate powder by a simple method, and by heating and dissolving barium hydroxide octahydrate (Ba (OH) 2 · 8H 2 O) containing crystal water, It was found that a highly active barium dissolving liquid can be produced, and that the fine liquid BaTiO 3 powder of high purity can be easily produced by reacting the dissolving liquid with titanium oxide (TiO 2 ) powder. Moreover, it is believed that this finding could extend the application to complex oxides similar to BaTiO 3 .
본 발명은 이러한 발견에 기초하여 이루어진 것으로, 본 발명에 따른 복합 산화물 분말의 제조 방법은, 일반식 ABO3로 표시되는 페로브스카이트 구조를 갖는 복합 산화물 분말의 제조 방법으로, 결정수를 함유한 A사이트 성분을 구성하는 원소의 수산화물을 가열하여 상기 A사이트 성분을 함유한 용해액을 생성하는 용해액 생성 공정과, 소정의 초미립자로 이루어지는 B사이트 성분을 구성하는 원소의 산화물 분말과 상기 용해액을 반응시켜서 반응 합성물을 생성하는 반응 공정을 포함하는 것을 특징으로 한다.The present invention has been made on the basis of these findings, and the method for producing a composite oxide powder according to the present invention is a method for producing a composite oxide powder having a perovskite structure represented by the general formula ABO 3 , containing crystal water. A dissolution solution generation step of heating a hydroxide of an element constituting the A-site component to produce a dissolution solution containing the A-site component, an oxide powder of the element constituting the B-site component composed of predetermined ultrafine particles, and the dissolution solution And a reaction step of reacting to produce a reaction compound.
그리고, 복합 산화물 분말로서 BaTiO3분말을 제조하는 경우에는, 수산화물로서 Ba(OH)2·8H2O를 사용할 수 있고, 초미립의 산화물 분말로서 TiO2분말을 사용할 수 있다.And, in the case of manufacturing a BaTiO 3 powder, a composite oxide powder, a hydroxide can be used. Ba (OH) 2 · 8H 2 O, TiO 2 powder may be used as the oxide powder of the ultra fine.
즉, 본 발명의 복합 산화물 분말의 제조 방법은, 상기 수산화물은 Ba(OH)2·8H2O이며, 상기 산화물 분말은 TiO2분말인 것을 특징으로 한다.That is, the method for producing a composite oxide powder of the present invention is characterized in that the hydroxide is Ba (OH) 2 · 8H 2 O, and the oxide powder is TiO 2 powder.
또한, 결정수를 함유한 상기 수산화물을 가열 처리하는 대신에, 결정수와 동등한 양의 물과 수산화물의 무수염을 혼합하여 용해액을 생성하여도, 상기 작용 효과를 발휘할 수 있다.In addition, instead of heat-treating the hydroxide containing crystalline water, the above-described effects can be exerted even if an aqueous solution of water and an anhydrous salt of the hydroxide is mixed in an amount equivalent to that of the crystalline water.
즉, 본 발명의 복합 산화물 분말의 제조 방법은, 일반식 ABO3로 표시되는 페로브스카이트 구조를 갖는 복합 산화물 분말의 제조 방법으로, A사이트 성분을 구성하는 원소의 수산화물 무수염과 소정량의 물을 혼합하여 A사이트 성분을 함유한 용해액을 생성하는 용해액 생성 공정과, 소정의 초미립자로 이루어지는 B사이트 성분을 구성하는 원소의 산화물 분말과 상기 용해액을 반응시켜서 반응 합성물을 생성하는 반응 공정을 포함하는 것을 특징으로 하고, 또한 상기 소정량의 물은 상기 수산화물이 결정수를 함유한 경우에 있어서의 상기 결정수와 동등한 수량(水量)인 것을 특징으로 한다.That is, the manufacturing method of the composite oxide powder of the invention, the formula in the manufacture of composite oxide powder having a perovskite structure represented by ABO 3 method, the hydroxide-free stubble with a predetermined amount of the element constituting the A site component A dissolution solution generation step of mixing a water to generate a dissolution solution containing an A-site component, and a reaction step of reacting an oxide powder of an element constituting a B-site component composed of predetermined ultrafine particles with the dissolution solution to generate a reaction compound. The predetermined amount of water is characterized in that the amount of water equivalent to the crystallized water in the case where the hydroxide contains the crystallized water.
그리고, 복합 산화물 분말로서의 BaTiO3분말을 제조하는 경우에는, 수산화물로서 Ba(OH)2를 사용할 수 있고, 초미립의 산화물 분말로서 TiO2분말을 사용할 수 있다.Further, in the case of manufacturing a BaTiO 3 powder of the composite oxide powder, the hydroxide can be used as a Ba (OH) 2, TiO 2 powder may be used as the oxide powder of the ultra fine.
즉, 본 발명의 복합 산화물 분말의 제조 방법은, 상기 수산화물은 Ba(OH)2이며, 상기 산화물 분말은 TiO2분말인 것을 특징으로 하는 것도 바람직하다.That is, in the method for producing the composite oxide powder of the present invention, the hydroxide is preferably Ba (OH) 2 , and the oxide powder is preferably TiO 2 powder.
또한, 최종 생성물인 복합 산화물 분말이 초미립 또한 고결정이기 위해서는, 소재가 되는 산화물 분말이 초미립이고 결정성이 우수한 것이 요구된다.In addition, in order that the composite oxide powder which is a final product is ultra fine and high crystal | crystallization, it is required that the oxide powder used as a raw material is ultra fine and excellent crystallinity.
그리고, 본 발명자들이 심도깊게 연구를 진행한 결과, 비표면적이 250m2/g 이상인 산화물 분말을 소재로 사용함으로써, 하소 전의 건조 분말 상태에서 이상(異相)의 생성을 피할 수 있고, 이것에 의해 초미립이고 결정성이 우수한 복합 산화물 분말을 제조할 수 있다는 것을 발견하였다.As a result of the in-depth study by the present inventors, by using an oxide powder having a specific surface area of 250 m 2 / g or more as a material, generation of abnormalities in the dry powder state before calcination can be avoided, thereby It has been found that composite oxide powders that are fine and have good crystallinity can be produced.
본 발명의 복합 산화물 분말의 제조 방법은, 상기 소정의 초미립자는 비표면적이 250m2/g 이상인 것을 특징으로 한다.The method for producing a composite oxide powder of the present invention is characterized in that the predetermined ultrafine particles have a specific surface area of 250 m 2 / g or more.
또한, 본 발명의 복합 산화물 분말의 제조 방법은, 상기 A사이트 성분과 상기 B사이트 성분의 비(A/B)가 몰비로 0.990∼1.010이 되도록, 상기 수산화물 및 상기 산화물 분말의 칭량을 조정하는 것을 특징으로 하고, 이것에 의해 불순물의 혼입 정도가 적은 고순도의 복합 산화물 분말을 제조할 수 있다.Moreover, the manufacturing method of the composite oxide powder of this invention adjusts the measurement of the said hydroxide and the said oxide powder so that ratio (A / B) of the said A-site component and said B-site component may be 0.990-1.010 by molar ratio. This makes it possible to produce a high purity composite oxide powder having a low degree of mixing of impurities.
또한, 본 발명의 복합 산화물 분말의 제조 방법은, 상기 반응 공정을 대기압 하에서 실행하는 것을 특징으로 하고, 이것에 의해 대규모의 특수 장치를 필요로 하지 않고, 원하는 복합 산화물 분말을 저렴한 가격으로 제조할 수 있다.Moreover, the manufacturing method of the complex oxide powder of this invention is characterized by performing the said reaction process under atmospheric pressure, by which it can manufacture a desired complex oxide powder at low price, without requiring a large-scale special apparatus. have.
또한, 본 발명자들의 실험 결과에 의해 상기 반응 공정에서 초음파 조사를 실시함으로써, 하소 전의 단계에서 비표면적이 60∼100m2/g으로 이루어지는 보다 한층 미립화된 반응 합성물을 생성할 수 있다는 것이 판명되었다.In addition, the experimental results of the present inventors showed that by performing ultrasonic irradiation in the above reaction step, it is possible to produce a further atomized reaction composite having a specific surface area of 60 to 100 m 2 / g in the step before calcination.
본 발명의 복합 산화물 분말의 제조 방법은, 상기 반응 공정이 초음파를 조사하는 조사 공정을 포함하는 것을 특징으로 하고, 상기 조사 공정을 거쳐 생성된 반응 합성물의 비표면적이 60∼100m2/g인 것을 특징으로 한다.The method for producing a composite oxide powder of the present invention is characterized in that the reaction step includes an irradiation step of irradiating ultrasonic waves, and the specific surface area of the reaction compound produced through the irradiation step is 60 to 100 m 2 / g. It features.
그리고, 상기 반응 합성물에 하소 처리를 실시함으로써, 초미립이고 결정성이 우수한 복합 산화물 분말을 제조할 수 있다.Then, by subjecting the reaction composite to calcination, a composite oxide powder having ultra fine grains and excellent crystallinity can be produced.
즉, 본 발명의 복합 산화물 분말의 제조 방법은, 상기 반응 합성물을 하소하여 상기 복합 산화물을 제조하는 하소 공정을 포함하는 것을 특징으로 한다.That is, the manufacturing method of the complex oxide powder of this invention is characterized by including the calcining process of calcining the said reaction compound and manufacturing the said complex oxide.
또한, 본 발명자들의 거듭된 심도깊은 연구의 결과, 상기 반응 합성물을 용매에 분해시킨 후, 소정 온도 이상의 고온에서 하소함으로써, 결정축인 c축과 a축의 비, 즉 축비(c/a)를 보다 한층 향상시킬 수 있다는 것이 판명되었다.As a result of the in-depth study by the present inventors, the reaction compound is decomposed into a solvent and then calcined at a high temperature of a predetermined temperature or more, thereby further improving the ratio of the c-axis to the a-axis, that is, the axial ratio (c / a), of the crystal axis. It turned out that it could.
본 발명의 복합 산화물 분말의 제조 방법은, 상기 반응 합성물을 용매에 분해하는 분해 공정과, 상기 분해 공정에서 분해된 상기 반응 합성물을 하소하여 상기 복합 산화물을 제조하는 하소 공정을 포함하는 것을 특징으로 한다.The method for producing a composite oxide powder of the present invention includes a decomposition step of decomposing the reaction compound in a solvent, and a calcination step of calcining the reaction compound decomposed in the decomposition step to produce the complex oxide. .
(발명의 실시형태)Embodiment of the Invention
다음으로 본 발명의 실시형태를 도면을 참조하면서 상세하게 설명한다.Next, embodiment of this invention is described in detail, referring drawings.
도 1은 본 발명에 따른 복합 산화물 분말의 제조 방법의 한 실시형태로서의 BaTiO3의 제조 방법을 나타내는 블럭 공정도이다.1 is a block process diagram showing a method for producing BaTiO 3 as an embodiment of the method for producing a composite oxide powder according to the present invention.
우선, 페로브스카이트 구조(일반식 ABO3)에 있어서, A사이트 성분을 구성하는 Ba의 수산화물이며 또한 결정수를 함유하는 것으로서, Ba(OH)2·8H2O를 준비하고, 또한 B사이트 성분을 구성하는 Ti의 산화물 분말로서, 비표면적(Sw)이 250m2/g 이상인 TiO2분말을 준비한다.First, in the perovskite structure (General Formula ABO 3 ), Ba (OH) 2 · 8H 2 O is prepared as a hydroxide of Ba constituting the A-site component and containing crystal water, and further, B-site. As an oxide powder of Ti constituting the component, a TiO 2 powder having a specific surface area (Sw) of 250 m 2 / g or more is prepared.
여기에서, 비표면적(Sw)이 250m2/g 이상인 TiO2분말을 준비한 것은 이하와 같은 이유에 기인한다.Here, the TiO 2 powder having a specific surface area Sw of 250 m 2 / g or more is prepared for the following reasons.
250m2/g 미만인 TiO2분말을 사용한 경우에는, 하소 전의 미하소 단계에서 Ba2TiO4나 BaTi2O5 등의 이상(異相)이 생성되고, 따라서 하소 전의 미하소 단계에서 결정성이 우수한 입방정 BaTiO3를 얻을 수 없고, 이 때문에 하소 처리를 실시하여도 미립 또한 고결정의 정방정 BaTiO3를 얻을 수 없게 된다.In the case of using TiO 2 powder of less than 250 m 2 / g, abnormalities such as Ba 2 TiO 4 or BaTi 2 O 5 are generated in the uncalcining step before calcination, and thus cubic crystals having excellent crystallinity in the uncalcination step before calcination BaTiO 3 cannot be obtained, and therefore, even when calcined, fine grain tetragonal BaTiO 3 cannot be obtained.
본 실시형태에서는 비표면적(Sw)이 250m2/g 이상인 TiO2분말을 사용하고, 이것에 의해 하소 후에는 미립 또한 고결정의 정방정 BaTiO3를 확실하게 얻을 수 있도록 하고 있다.In the present embodiment, TiO 2 powder having a specific surface area (Sw) of 250 m 2 / g or more is used, whereby after calcining, it is possible to reliably obtain fine grains and tetragonal tetragonal BaTiO 3 .
TiO2의 결정 구조는 루틴형 구조, 아나타제형 구조 중 어느 것이여도 되지만, 루틴형 구조의 TiO2를 사용한 경우에는 미반응의 TiO2가 잔류할 우려가 있기 때문에, 아나타제형 구조의 TiO2를 사용하는 것이 바람직하다.The crystal structure of TiO 2 may be either a rutin type structure or an anatase type structure. However, when TiO 2 having a rutin type structure is used, unreacted TiO 2 may remain. Therefore, TiO 2 having an anatase type structure is used. It is desirable to.
이렇게 Ba(OH)2·8H2O 및 TiO2분말을 준비한 후, 혼합 처리 공정(1)으로 진행한다.Thus, Ba (OH) 2 · 8H 2 O and TiO 2 powder is prepared, and then proceeds to the mixing treatment step (1).
혼합 처리 공정(1)은 용해액 생성 공정(1a)과 반응 공정(1b)으로 구분된다.The mixing treatment step (1) is divided into a dissolution solution generation step (1a) and a reaction step (1b).
용해액 생성 공정(1a)에서는, 합성된 BaTiO3의 Ba와 Ti의 몰비(Ba/Ti)가 1이 되도록 Ba(OH)2·8H2O 및 TiO2를 칭량한다. 이들 칭량물을 용기에 투입하여 혼합하고, 소정 온도(예를 들면, 60∼110℃)에서 가열 처리를 실시하여 Ba용해액을 생성한다.In the solution formation step (1a), Ba (OH) 2 .8H 2 O and TiO 2 are weighed so that the molar ratio (Ba / Ti) of Ba and Ti of synthesized BaTiO 3 is 1. These weighed materials are added to a container, mixed, and heat-treated at a predetermined temperature (for example, 60 to 110 ° C.) to generate a Ba solution.
즉, Ba(OH)2·8H2O 안에는 결정수(8수화물)가 함유되어 있기 때문에, 상기 가열 처리를 실시하면 결정수의 수분량만으로 Ba가 용해되어, Ba2+를 함유한 반응 활성인 고농도의 Ba용해액이 생성된다.That is, since Ba (OH) 2 · 8H 2 O contains crystalline water (octahydrate), when the heat treatment is carried out, Ba is dissolved only by the water content of the crystalline water, and a high concentration of reaction activity containing Ba 2+ is achieved. Ba Ba solution is produced.
그리고, 반응 공정(1b)에서는, Ba용해액과 TiO2를 대기압 하에서 반응시키고, 이것에 의해 소정 시간(예를 들면, 약 1시간) 경과 후에는 슬러리 형상의 BaTiO3(반응 합성물)가 생성된다.In the reaction step (1b), the Ba solution and TiO 2 are allowed to react under atmospheric pressure, whereby a slurry-like BaTiO 3 (reaction compound) is produced after a predetermined time (for example, about 1 hour) has elapsed. .
즉, 용해액 생성 공정(1a) 및 반응 공정(1b)은 연속적으로 진행되어, 화학식(1)에 나타낸 바와 같이 Ba(OH)2·8H2O와 TiO3로부터 슬러리 형상의 BaTiO3가 생성된다.That is, the dissolution solution generation step (1a) and the reaction step (1b) proceed continuously, and as shown in the formula (1), a slurry-like BaTiO 3 is formed from Ba (OH) 2 .8H 2 O and TiO 3 . .
그런데, BaTiO3의 합성 반응 경로로서는 도 2에 나타낸 합성 경로(이하, 합성 경로(1)라 한다)와, 도 3에 나타낸 합성 경로(이하, 합성 경로(2)라 한다)가 존재하는 것이 알려져 있다(J.O.Eckert Jr, et al., J.Am.Ceram.Soc., 79[11]2929-39(1996)).By the way, it is known that the synthetic reaction path of BaTiO 3 exists as a synthetic route shown in FIG. 2 (hereinafter referred to as a synthetic route 1) and a synthetic route shown in FIG. 3 (hereinafter referred to as a synthetic route 2). (JOEckert Jr, et al., J. Am. Ceram. Soc., 79 [11] 2929-39 (1996)).
즉, 합성 경로(1)는 균일핵 생성 반응(a)과 불균일핵 생성 반응(b)이 병렬적으로 진행되어, TiO2가 Ba용해액 안에 용해하여 BaTiO3를 생성하고, 합성 경로(2)는 TiO2입자 내부로의 Ba의 확산에 의해 BaTiO3를 생성한다.That is, in the synthesis route 1, the homogeneous nucleation reaction (a) and the heterogeneous nucleation reaction (b) proceed in parallel, and TiO 2 dissolves in the Ba solution to generate BaTiO 3 , and the synthesis route (2) Produces BaTiO 3 by diffusion of Ba into TiO 2 particles.
그리고, TiO2의 용해도는 낮고 BaTiO3의 임계 과포화도가 높기 때문에, BaTiO3가 핵생성한 후의 입자 성장은 극히 느리다. 따라서 반응 초기에는 합성 경로(1)가 우선적으로 진행되고, 반응 후기에는 합성 경로(2)가 우세해진다고 생각된다.And, since the solubility of the TiO 2 is low and a high degree of supersaturation threshold of BaTiO 3, BaTiO 3 particles grow after the generation nucleus is extremely slow. Therefore, it is thought that the synthesis route 1 preferentially proceeds at the beginning of the reaction, and the synthesis route 2 prevails at the later stage of the reaction.
그러나, 본 실시형태에서는 250m2/g 이상의 큰 비표면적(Sw)을 갖는 TiO2분말을 사용하고 있기 때문에, TiO2의 용해는 빠르게 진행되고, 그 결과 입자 성장에 필요한 침전종(沈殿種)이 충분히 공급되어, 합성 반응은 합성 경로(1)에 의해 거의 완료된다.However, in the present embodiment, since TiO 2 powder having a large specific surface area (Sw) of 250 m 2 / g or more is used, dissolution of TiO 2 proceeds rapidly, and as a result, precipitated species required for grain growth are formed. With sufficient supply, the synthesis reaction is almost complete by the synthesis route 1.
TiO2의 비표면적(Sw)이 커짐에 따라서 TiO2의 용해는 빠르게 진행되기 때문에, TiO2의 비표면적(Sw)은 커지면 커질수록, 합성 경로(1)의 합성 반응은 빠르게 완료되어 BaTiO3가 생성된다. 따라서, 비표면적(Sw)은 적어도 250m2/g 이상이면 되고, 상한값은 특별히 한정되는 것은 아니다.Since the specific surface area (Sw) of the TiO 2 is in accordance with the increases dissolution of the TiO 2 is speeding up, the more the specific surface area (Sw) of TiO 2 is greater larger, the synthesis reaction of the synthesis route 1 is quickly completed, the BaTiO 3 Is generated. Therefore, the specific surface area Sw should just be 250 m <2> / g or more at least, and an upper limit is not specifically limited.
다음으로 슬러리 제조 공정(2)으로 진행한다. 반응 공정(1b)에서 생성된 반응 합성물로서의 BaTiO3를 분쇄 매체가 포함된 샌드밀에 투입하여, 상기 소정 온도(예를 들면, 60∼110℃)의 가열 상태를 유지한 채로 혼합 분쇄하고, 슬러리를 제조하여 배출한다.Next, the process proceeds to slurry production step (2). BaTiO 3 as a reaction compound produced in the reaction step (1b) was introduced into a sand mill containing a grinding medium, mixed and ground while maintaining the heating state at the predetermined temperature (for example, 60 to 110 ° C.), and a slurry Prepare and discharge.
이어서, 건조 공정(3)으로 진행한다. 배출된 슬러리를 소정 온도(예를 들면, 200℃)로 가열한 오븐 안에 넣어 수분을 증발 건조시키고, 이것에 의해 비표면적 구상당 직경(球相當徑; sphere-equivalent diameter)이 약 20nm인 BaTiO3분말을 제조한다.Next, it progresses to the drying process (3). The discharged slurry was placed in an oven heated to a predetermined temperature (for example, 200 ° C.) to evaporate and dry moisture, thereby allowing BaTiO 3 having a specific surface-equivalent diameter of about 20 nm. Prepare a powder.
그리고, 이어지는 하소 공정(4)에서는 900℃∼1000℃에서 약 2시간 하소하고, 이것에 의해 입자는 입자 성장하여, 비표면적 구상당 직경은 100∼350nm정도가 되며, 결정계가 변화하여 정방정계의 고순도이고 초미립인 BaTiO3분말을 얻는다.In the subsequent calcination step (4), the particles are calcined at 900 ° C to 1000 ° C for about 2 hours, whereby the particles grow to particles, the diameter per spherical specific surface area is about 100 to 350 nm, and the crystal system changes to form a tetragonal system. A high purity, ultrafine BaTiO 3 powder is obtained.
이렇게 하여 제조된 BaTiO3분말은 결정축인 c축과 a축의 축비(c/a)가 1.0068∼1.0092인 정방정계를 갖으며, 이상이 적고 결정성이 우수한 것이 된다.The BaTiO 3 powder thus prepared has a tetragonal system having an axial ratio (c / a) of 1.0068 to 1.0092 of the c-axis and the a-axis, which are the crystal axes, with less abnormality and excellent crystallinity.
또한, 상기 BaTiO3분말은 A사이트 성분인 Ba와 B사이트 성분인 Ti와의 몰비(Ba/Ti)가 0.990∼1.010이 되고, 불순물의 혼입이 적은 고순도의 BaTiO3분말을 얻을 수 있다.In addition, the BaTiO 3 powder has a molar ratio (Ba / Ti) between Ba as an A-site component and Ti as a B-site component of 0.990 to 1.010, thereby obtaining a high-purity BaTiO 3 powder having little impurities.
또한, 본 실시형태에서는 반응 활성이고 고농도인 Ba용해액을 제조함으로써, 충분히 고농도인 수산화물 이온이 얻어지며, 따라서 알칼리 금속 등의 원소의 첨가를 필요로 하지 않고 BaTiO3분말을 제조할 수 있다.In addition, in this embodiment, by producing a highly active and highly concentrated Ba solution, hydroxide ions which are sufficiently high in concentration can be obtained, and thus BaTiO 3 powder can be produced without requiring addition of an element such as an alkali metal.
또한, 본 실시형태에서는 위험물에 해당하는 알콕시드나 과잉 알칼리를 사용할 필요가 없기 때문에, 알콕시드 수산화물법과 같은 방폭 설비도 불필요하며, 또한 60∼110℃정도의 저온에서 가열 처리를 실시하고, 또한 대기압 하에서 반응 처리를 실시할 수 있기 때문에, 수열 합성법과 같은 내압 설비도 불필요하여 저렴하게 제조할 수 있다.In addition, in this embodiment, since it is not necessary to use the alkoxide or excess alkali which correspond to a dangerous goods, explosion-proof equipment, such as an alkoxide hydroxide method, is also unnecessary, and heat-processes at the low temperature of about 60-110 degreeC, and also under atmospheric pressure Since the reaction treatment can be performed, pressure-resistant facilities such as hydrothermal synthesis are also unnecessary and can be manufactured at low cost.
이렇게 본 실시형태에서는 Ba(OH)2·8H2O와 초미립의 TiO2분말을 가열하여 반응시킴으로써, 이상을 포함하지 않고 결정성이 우수한 초미립의 BaTiO3를 저렴한 가격으로 용이하게 얻을 수 있다.So by reacting this embodiment, by heating the Ba (OH) 2 · 8H 2 O and ultrafine TiO 2 powder, it is possible to readily obtain the crystallinity BaTiO excellent ultrafine does not include more than 3 at a low price .
게다가 본 실시형태에서는 제조 공정이 간소하기 때문에, 용이하게 공정의 연속화를 도모할 수 있고, 생산 효율도 좋다. 즉, 양산성도 우수하고, 고품질의 BaTiO3분말을 저렴하게 대량으로 합성할 수 있다.Moreover, in this embodiment, since a manufacturing process is simple, the process can be easily serialized and production efficiency is also good. That is, it can be excellent in mass-production Chengdu and inexpensively synthesized in large quantities of high quality BaTiO 3 powder.
본 발명은 상기 실시형태에 한정되는 것이 아니다. 상기 실시형태에서는 결정수를 함유한 Ba(OH)2·8H2O를 가열 용해시켜서 반응 활성인 고농도의 Ba용해액을 생성하고 있으나, 상기 결정수와 동등한 양의 물과 수산화 바륨 무수염(Ba(OH)2)을 혼합시킴으로써도 반응 활성인 고농도의 Ba용해액을 생성할 수 있고, 상기와 같은 고결정 또한 미립인 BaTiO2분말을 생성할 수 있다.This invention is not limited to the said embodiment. In the above embodiment, Ba (OH) 2 · 8H 2 O containing crystallized water is heated to dissolve to produce a high concentration of Ba solution having a reaction activity. However, the same amount of water and barium hydroxide anhydride (Ba By mixing (OH) 2 ), it is possible to produce a high concentration of Ba solution having a reaction activity, and to produce BaTiO 2 powder which is also a high crystal as described above.
또한, 상기 실시형태에서는, 반응 공정(1b)에서 Ba용해액과 TiO2를 반응시켜서 슬러리 형상의 BaTiO3(반응 합성물)를 생성하고 있으나, 상기 슬러리 형상의 BaTiO3를 교반하는 한편, 주파수 10∼30kHz의 초음파를 상기 슬러리 형상의 BaTiO3에 조사하여 반응 합성물을 생성하는 것도 바람직하고, 이러한 초음파의 조사에 의해 하소 전의 단계에서, 이상을 포함하지 않고 비표면적(Sw)이 60∼100m2/g인 보다 한층 미립화된 입방정 BaTiO3를 얻을 수 있다.In the above embodiment, by reaction of the Ba solution was and TiO 2 in the reaction process (1b) produce a BaTiO 3 (reaction compound), the slurry-like. However, to stir the BaTiO 3 of the slurry-like hand, frequency 10 to It is also preferable to generate a reaction compound by irradiating ultrasonic wave of 30 kHz to the slurry-shaped BaTiO 3 , and in the step before calcination by irradiation of such ultrasonic wave, the specific surface area (Sw) is 60-100 m 2 / g without any abnormality. Cubic BaTiO 3 finer than phosphorus can be obtained.
상기 실시형태에서는 BaTiO3분말을 제조하는 방법에 대하여 상세하게 서술하였으나, 이러한 BaTiO3분말과 동일한 페로브스카이트 구조를 갖는 복합 산화물, 예를 들면 SrTiO3나 (Ba, Ca)TiO3 등에도 적용할 수 있다.In the above embodiment, a method for producing BaTiO 3 powder has been described in detail, but the present invention is also applied to a composite oxide having the same perovskite structure as BaTiO 3 powder, for example, SrTiO 3 or (Ba, Ca) TiO 3 . can do.
<실시예><Example>
다음으로, 본 발명의 실시예를 구체적으로 설명한다.Next, embodiments of the present invention will be described in detail.
(제 1 실시예)(First embodiment)
본 발명자들은 우선 BaTiO3의 합성 반응 경로를 검증하였다.The present inventors first verified the synthesis reaction route of BaTiO 3 .
즉, 합성 반응에서 생성된 BaTiO3(반응 합성물)의 Ba와 Ti의 몰비(Ba/Ti)가 1이 되도록, 비표면적(Sw)이 330m2/g인 아나타제형 TiO2 및 Ba(OH)2·8H 2O를 각각 57.342g, 202.88g 칭량하여, 온도 70℃로 가열한 용기에 칭량물을 투입하고 대기압 하에서 1시간 가열하여 반응시켜서, BaTiO3의 생성 과정을 관찰하였다.That is, anatase type TiO 2 and Ba (OH) 2 having a specific surface area (Sw) of 330 m 2 / g so that the molar ratio (Ba / Ti) of Ba and Ti of BaTiO 3 (reaction compound) produced in the synthesis reaction is 1 57.342 g and 202.88 g of 8H 2 O were weighed, respectively, and a weighed product was added to a vessel heated to a temperature of 70 ° C. and heated and reacted for 1 hour under atmospheric pressure to observe the formation process of BaTiO 3 .
도 4∼도 6은 BaTiO3의 합성 반응 과정에 있어서의 결정 상태를 투과형 전자 현미경(TEM)으로 촬영한 사진이다.4 to 6 are photographs taken with a transmission electron microscope (TEM) of the crystal state in the BaTiO 3 synthesis reaction process.
즉, 도 4는 칭량물을 용기에 투입하고, 반응을 개시하고 나서 5분 경과하였을 때의 결정 상태를 TEM으로 배율 79만배로 촬영한 것이다. 또한, 도 5 및 도 6은 도 4의 ○부로 나타낸 분석 영역에 대하여, 반응 개시 후 30분 및 60분 경과하였을 때의 결정 상태를 TEM으로 배율 39만배로 촬영한 것이다.That is, FIG. 4 is a photographed at 790,000-fold magnification of the crystalline state when 5 minutes have passed since the weighed product was put into a container and the reaction was started. 5 and 6 show a TEM of 390,000 times the crystalline state when 30 minutes and 60 minutes have elapsed after the start of the reaction, for the analysis region indicated by a part of FIG. 4.
도 4∼도 6으로부터, 최초에는 입자 직경이 5nm정도의 TiO2분말이 반응의 진행에 따라 커져서 20nm정도의 입자 직경을 갖는 BaTiO3가 되는 것을 알 수 있었다.Also from Fig. 4 to 6, the first has been found that the BaTiO 3 particles having a diameter of about particle size is large, with the progress of the TiO 2 powder of about 5nm 20nm reaction.
또한, EDX(에너지 분산형 X선 회절 장치)로 Ba와 Ti의 몰비(Ba/Ti)를 측정하였더니, 반응을 개시하고 나서 5분 후에는 몰비(Ba/Ti)가 6/29이지만(도 4), 반응을 개시하고 나서 30분 후에는 몰비(Ba/Ti)가 19/20으로 거의 같은 몰이 되고 있는 것을 알 수 있었다(도 5).In addition, the molar ratio (Ba / Ti) of Ba and Ti was measured by an EDX (energy dispersive X-ray diffractometer). The molar ratio (Ba / Ti) was 6/29 5 minutes after the start of the reaction (Fig. 4) It was found that 30 minutes after the start of the reaction, the molar ratio (Ba / Ti) became almost the same mole of 19/20 (FIG. 5).
합성 경로로서는 상기에 기재한 바와 같이, 도 2에 나타낸 합성 경로(1)와, 도 3에 나타낸 합성 경로(2)가 있는데, 이들 일련의 반응 과정(도 4∼도 6)에 있어서의 입자는 모두 단결정을 나타내고 있고, Ba가 일부 확산된 것과 같은 입자는 발견되지 않으며, 이러한 것으로부터 합성 경로(1)의 반응 수행에 의해 합성 반응은 거의 완료되고 있다고 추측된다.As described above, as described above, there are a synthetic route 1 shown in FIG. 2 and a synthetic route 2 shown in FIG. 3. Particles in the series of reaction processes (FIGS. All of them show a single crystal, and no particles such as Ba partially diffused are found. From this, it is assumed that the synthesis reaction is almost completed by performing the reaction of the synthesis route (1).
(제 2 실시예)(Second embodiment)
다음으로 본 발명자들은 제 1 실시예와 같이 하여 생성한 슬러리 형상의 BaTiO3(반응 합성물)와 분쇄 매체인 1mmø의 PSZ(Partial Stabilized Zirconia; 부분 안정화 지르코니아) 800g을 탁상형 샌드밀에 투입하고, 가열 온도를 70℃로 유지하면서, 회전 속도 9/s-1(회전수 540rpm)로 1시간 혼합하고 습식 분쇄하여, 슬러리를 제조하였다. 그리고 그 후, 슬러리를 배출하여 200℃로 가열한 오븐 안으로 반송하고, 상기 오븐 안에서 수분을 증발 건조시켜서 고형물 형상으로 한 후, 온도 900℃, 950℃, 1000℃에서 각각 2시간 소성 처리를 실시하여, BaTiO3분말(하소 분말)을 얻었다(실시예 1). 얻어진 BaTiO3분말 중의 Ba와 Ti의 몰비(Ba/Ti)를 형광 X선 분석(XRF)으로 측정하였더니 0.998이였다.Next, the inventors put a slurry-like BaTiO 3 (reaction compound) produced in the same manner as in the first embodiment and 800 g of PSZ (Partial Stabilized Zirconia) with a milling medium of 1 mm ø into a table-type sand mill and heated it. While maintaining the temperature at 70 ° C., the mixture was mixed at a rotational speed of 9 / s −1 (rotational speed of 540 rpm) for 1 hour and wet pulverized to prepare a slurry. After that, the slurry was discharged and conveyed into an oven heated to 200 ° C, the water was evaporated to dryness in the oven to form a solid, and then calcined at 900 ° C, 950 ° C, and 1000 ° C for 2 hours, respectively. , BaTiO 3 powder (calcined powder) was obtained (Example 1). The molar ratio (Ba / Ti) of Ba and Ti in the obtained BaTiO 3 powder was 0.998 when measured by fluorescence X-ray analysis (XRF).
다음으로, 본 발명자들은 실시예 1의 BaTiO3분말에 대하여 각 하소 온도 마다 BET법으로 비표면적(Sw)을 측정하고, 상기 비표면적(Sw)으로부터 비표면적 구상당 직경(D)을 산출하였다. 또한, 분말 X선 회절법(XRD)으로 X선 회절을 실시하고, 그 분석 결과에 기초하여 결정축의 c축과 a축의 축비(c/a)를 산출하였다. 상기 200℃에서 건조시킨 200℃ 건조품(미하소품)에 대해서도 상기와 동일한 측정을 실시하였다.Next, the present inventors have calculated the embodiment with respect to BaTiO 3 powder of Example 1, each calcined measuring the specific surface area (Sw) by the BET method, and the equivalent sphere surface area from the surface area (Sw) diameter (D). In addition, X-ray diffraction was performed by powder X-ray diffraction (XRD), and the ratio (c / a) of the c-axis and a-axis of the crystal axis was calculated based on the analysis result. Measurement similar to the above was performed also about the 200 degreeC dry goods (uncalculated goods) dried at the said 200 degreeC.
표 1에 그 측정 결과를 나타낸다.Table 1 shows the measurement results.
표 1로부터 알 수 있듯이, 미하소품의 BaTiO3는 비표면적(Sw)이 47.61m2/g이고 비표면적 구상당 직경(D)이 21.0nm으로 작으며, 축비(c/a)도 1.0000으로 입방정계이다.As can be seen from Table 1, untired BaTiO 3 has a specific surface area (Sw) of 47.61 m 2 / g, a specific surface area spherical diameter (D) of 21.0 nm, and an axial ratio (c / a) of 1.0000. It is a system.
그리고, 하소함으로써 입자 성장이 발생하여 입자 직경이 커지고, 또한 이러한 입자 직경이 커짐에 따라서, 축비(c/a)도 커져서 결정계는 입방정계로부터 정방정계로 전이하고 있다는 것을 알 수 있다.As calcination occurs, grain growth occurs, the grain diameter increases, and as the grain diameter increases, the axial ratio c / a also increases, indicating that the crystal system is transitioning from a cubic system to a tetragonal system.
도 7∼도 10은 미하소품(200℃ 건조품), 900℃ 하소품, 950℃ 하소품, 1000℃ 하소품의 각각의 상태를 주사형 전자 현미경(SEM)으로 촬영한 사진이다.7-10 is the photograph which image | photographed the state of each uncalcined product (200 degreeC dried product), 900 degreeC calcined product, 950 degreeC calcined product, and 1000 degreeC calcined product with a scanning electron microscope (SEM).
도 7∼도 10에 나타낸 바와 같이 하소 온도가 높아지면, 입자 성장이 진행되어 입자 직경이 커져 가는 것을 알 수 있다.As shown in FIGS. 7-10, when calcination temperature becomes high, it turns out that particle growth advances and particle diameter becomes large.
도 11은 X선 회절의 측정 결과를 나타내는 특성도로서, 횡축은 회절각 2θ(°), 종축은 강도(임의 단위)이다. 또한, 도면 중에 △는 반응 과정에 있어서 부생성물로서 생길 수 있는 BaCO3, ■는 BaTiO3보다도 Ba성분에 풍부한 Ba2 TiO4를 각각 나타내고 있다.11 is a characteristic diagram showing a measurement result of X-ray diffraction, the horizontal axis is diffraction angle 2θ (°), and the vertical axis is intensity (arbitrary unit). In the drawings, Δ represents BaCO 3 and ■, which may occur as by-products in the reaction process, and Ba 2 TiO 4, which is more abundant in the Ba component than BaTiO 3 , respectively.
도 11에서 알 수 있듯이, 미하소품이라도 입방정 BaTiO3의 피크가 생기고, 따라서 70℃의 저온에서 합성하여도 결정성이 우수한 입방정 BaTiO3를 생성할 수 있고, 또한 BaCO3나 Ba2TiO4 등의 이상은 거의 부차적으로 생성되지 않는 것을 알 수 있다.Etc. As can be seen from 11, Mihama small even if it is possible to occurring of the cubic BaTiO 3 peak, and thus create a degree cubic BaTiO 3 having excellent crystallinity by synthesis at a low temperature of 70 ℃, also BaCO 3 and Ba 2 TiO 4 of It can be seen that the abnormality is hardly generated secondaryly.
즉, 분쇄법 등의 종래의 합성법과는 달리, 본 실시예에서는 하소 전의 미하소 단계에서 초미립의 결정성이 우수한 입방정 BaTiO3를 합성할 수 있고, 그 결과 하소 후에는 미립 또한 고결정성의 정방정 BaTiO3 분말을 얻을 수 있다.In other words, unlike conventional synthesis methods such as pulverization, in the present embodiment, cubic BaTiO 3 having excellent crystallinity of ultrafine grains can be synthesized in the uncalcining step before calcination, and as a result, after calcination, fine grains and highly crystalline tetragons are obtained. A positive BaTiO 3 powder can be obtained.
다음으로 본 발명자들은 수열 합성법을 사용하여 비교예 1의 BaTiO3분말을 제조하고, 또한 알콕시드 수산화물법을 사용하여 비교예 2의 BaTiO3분말을 제조하여, 상기 실시예 및 비교예 1, 2의 BaTiO3의 입자 직경과 축비(c/a)의 관계를 조사하였다.Next, the present inventors have manufactured a BaTiO 3 powder of Comparative Example 1 using the hydrothermal method also alkoxide using a hydroxide method to prepare a BaTiO 3 powder of Comparative Example 2, the above Example and Comparative Examples 1 and 2 The relationship between the particle diameter of BaTiO 3 and the axial ratio (c / a) was investigated.
비교예 1의 BaTiO3분말은 구체적으로는 이하와 같이 제조하였다.BaTiO 3 powder of Comparative Example 1 was specifically prepared as follows.
우선, 10㎖의 순수에 0.01몰의 NaOH를 용해시켜서 NaOH 수용액을 제조하고, 이어서 2.5㎖의 BaCl2 또는 Ba(OH)2와, 2.5㎖의 TiO2를 상기 NaOH수용액에 첨가하였다. 그 후, 오토클레이브 내에서 가열하고, 온도 250℃, 압력 5MPa의 고온 고압하에서 반응시켜서 침전물을 여과한 후, 순수로 세정하였다.First, 0.01 mol of NaOH was dissolved in 10 ml of pure water to prepare an aqueous NaOH solution, and then 2.5 ml of BaCl 2 or Ba (OH) 2 and 2.5 ml of TiO 2 were added to the aqueous NaOH solution. Thereafter, the mixture was heated in an autoclave, reacted under a high temperature and a high pressure of a temperature of 250 ° C., and a pressure of 5 MPa to filter the precipitate, and then washed with pure water.
생성물을 XRD로 X선 회절을 실시하였더니, 미반응의 TiO2 및 BaCO3는 검출되지 않았다.When the product was subjected to X-ray diffraction with XRD, unreacted TiO 2 and BaCO 3 were not detected.
그리고 그 후, BaCl2를 이용하여 일주일간 반응시켜서 입자 직경 50nm의 정방정 BaTiO3를 제조하고, 그 후 900℃, 950℃, 1000℃에서 각각 하소하여 비교예 1의 BaTiO3분말을 제조하였다.Then, BaCl 2 was reacted for one week using BaCl 2 to prepare tetragonal BaTiO 3 having a particle diameter of 50 nm, and then calcined at 900 ° C., 950 ° C. and 1000 ° C., respectively, to prepare BaTiO 3 powder of Comparative Example 1.
또한, 비교예 2의 BaTiO3분말은 이하와 같이 제조하였다,.In addition, BaTiO 3 powder of Comparative Example 2 was prepared as follows.
우선, 합성 반응으로 생성된 BaTiO3(반응 합성물)의 Ba와 Ti의 몰비(Ba/Ti)가 1이 되도록, 온도 60℃로 유지한 2.5×103mol/m3의 Ti[OCH(CH3) 2]4(티탄 이소프로폭시드)에 Ba(OH)2·8H2O 분말을 투입하고, 심하게 교반하였다. Ba(OH)2 의 용해에 의해 용액이 균일해진 후, 3분 경과 후에 용액이 백탁하여 겔화되었다. 겔화된 슬러리 형상 용액의 적외선 흡수 스펙트럼을 측정하였더니, 380cm-1, 570cm-1에 흡수대(吸收帶)가 확인되었으며, 이것에 의해 겔 중에 페로브스카이트형 구조를 갖는 화합물이 생성되고 있다는 것을 알 수 있었다.First, Ti [OCH (CH 3) of 2.5 × 10 3 mol / m 3 maintained at a temperature of 60 ° C. such that the molar ratio (Ba / Ti) of Ba and Ti of BaTiO 3 (reaction compound) produced by the synthesis reaction was 1. ) 2 ] 4 Ba (OH) 2 8H 2 O powder was added to (titanium isopropoxide), followed by vigorous stirring. After the solution became uniform by dissolution of Ba (OH) 2, the solution became cloudy and gelated after 3 minutes. Was measured for infrared absorption spectrum of the gel-like solution, slurry, 380cm -1, was verified by absorption band (吸收帶) to 570cm -1, it understood that the compounds having a structure Perovskite - Type Fe lobe is generated in the gel by this Could.
이어서, 상기 슬러리 형상 용액을 온도 150℃로 가열한 오븐 안에서 2시간 건조하여, 입자 직경 48nm의 BaTiO3분말을 제조하였다. BaTiO3분말을 XRF로 X선 회절을 실시하였더니, 몰비(Ba/Ti)는 0.998, 비표면적(Sw)은 45m2/g이였다. 그리고, 그 후 900℃, 950℃, 1000℃에서 각각 하소하여 비교예 2의 BaTiO3분말을 제조하였다.Subsequently, the slurry solution was dried in an oven heated to a temperature of 150 ° C. for 2 hours to prepare BaTiO 3 powder having a particle diameter of 48 nm. X-ray diffraction of BaTiO 3 powder by XRF showed a molar ratio (Ba / Ti) of 0.998 and a specific surface area (Sw) of 45 m 2 / g. Then, calcining was performed at 900 ° C, 950 ° C, and 1000 ° C, respectively, to prepare BaTiO 3 powder of Comparative Example 2.
도 12는 각 하소 후의 BaTiO3의 입자 직경과 축비(c/a)의 관계를 비교예와 함께 나타낸 특성도로서, 도면 중에서 ○는 실시예 1, ◆는 비교예 1, □는 비교예 2를 나타내고 있다.Fig. 12 is a characteristic diagram showing the relationship between the particle diameter and the axial ratio (c / a) of BaTiO 3 after each calcining with a comparative example, in which Fig. 1 is Example 1, ◆ is Comparative Example 1, and □ is Comparative Example 2; It is shown.
도 12로부터 알 수 있듯이, 실시예 1은 비교예 1에 비해 축비(c/a)도 높고, 미립이고 결정성이 우수한 정방정 BaCO3를 얻을 수 있다는 것을 알 수 있다.As can be seen from FIG. 12, it can be seen that Example 1 can obtain tetragonal BaCO 3 having a higher axial ratio (c / a) and finer grains and better crystallinity than Comparative Example 1. FIG.
또한, 비교예 2와 같은 알콕시드 수산화물법은 실시예 1보다도 미립이고 결정성이 양호하지만, TiO2에 대한 Ba(OH)2의 사용량을 2∼3배의 몰비로 해야하며, TiO2에 비해 과잉의 Ba(OH)2를 사용할 필요가 있다.In addition, the alkoxide method hydroxide such as Comparative Example 2 and Example 1 of all particulate and crystallinity is good, but the amount of 2-3 Ba (OH) 2 on TiO 2 have a molar ratio of the times, relative to TiO 2 Excess Ba (OH) 2 needs to be used.
이에 비해, 실시예 1에서는 TiO2와 Ba(OH)2의 사용량은 거의 동등한 몰로 반응이 완결되므로, 과잉의 Ba(OH)2를 사용할 필요도 없다. 따라서 상기 합성 반응 후에도 용액 안에 Ba2+가 잔존하지 않고, BaTiO3의 조성 억제도 용이하며, 저비용으로 제조할 수 있다.On the other hand, in Example 1, since TiO 2 and Ba (OH) 2 are used in almost equal molar amounts, the reaction is completed, and there is no need to use excess Ba (OH) 2 . Therefore, even after the synthesis reaction, Ba 2+ does not remain in the solution, and the composition of BaTiO 3 can be easily suppressed and can be manufactured at low cost.
(제 3 실시예)(Third embodiment)
본 발명자들은 비표면적(Sw)이 다른 TiO2분말을 사용하여 BaTiO3분말을 제조하고, X선 회절을 실시하여 이상의 생성 유무를 조사하였다.The present inventors prepared BaTiO 3 powder using TiO 2 powders having different specific surface areas (Sw), and performed X-ray diffraction to investigate the presence of abnormalities.
우선, 비표면적(Sw)이 250m2/g인 아나타제형 TiO2분말을 준비하고, 합성 반응에서 생성된 BaTiO3의 Ba와 Ti의 몰비(Ba/Ti)가 1이 되도록, 이들 TiO2분말 및 Ba(OH)2·8H2O를 각각 62.410g 및 119.77g 칭량하였다.First, anatase-type TiO 2 powders having a specific surface area (Sw) of 250 m 2 / g were prepared, and these TiO 2 powders and the molar ratio (Ba / Ti) of Ba and Ti of BaTiO 3 produced in the synthesis reaction were 1, and 62.410 g and 119.77 g of Ba (OH) 2 8 H 2 O were weighed, respectively.
이어서, 이 칭량물과 1mmø의 PSZ 800g을 탁상형 샌드밀에 투입하고, 제 2실시예과 거의 동일하게 가열 온도를 70℃로 유지하면서, 회전 속도 9/s-1로 1시간 혼합하고 습식 분쇄하여 슬러리를 제조하였다. 그리고 그 후, 슬러리를 배출하여 200℃로 가열한 오븐 안으로 반송하고, 상기 오븐 안에서 수분을 증발 건조시켜서, 실시예 11의 고형물 형상 BaTiO3를 제조하였다.Subsequently, this weighing material and 800 g of PSZ of 1 mm ø were put into a table-type sand mill, mixed with a rotational speed of 9 / s -1 for 1 hour, and wet-pulverized, while maintaining the heating temperature at 70 ° C. in substantially the same manner as the second embodiment. Slurry was prepared. Then, after that, the slurry was discharged and conveyed into an oven heated to 200 ° C., and water was evaporated to dryness in the oven to prepare solid BaTiO 3 of Example 11.
마찬가지로 비표면적(Sw)이 300m2/g인 아나타제형 TiO2분말을 준비하고, 합성 반응에서 생성된 BaTiO3의 Ba와 Ti의 몰비(Ba/Ti)가 1이 되도록, 이들 TiO2분말 및 Ba(OH)2·8H2O를 각각 189.28g 및 56.898g 칭량하여, 실시예 11과 동일한 방법·순서로 실시예 12의 고형물 형상 BaTiO3를 제조하였다.Similarly, anatase-type TiO 2 powders having a specific surface area (Sw) of 300 m 2 / g were prepared, and these TiO 2 powders and Ba were prepared so that the molar ratio (Ba / Ti) of Ba and Ti of BaTiO 3 produced in the synthesis reaction was 1. (OH) 2 .8H 2 O was weighed 189.28 g and 56.898 g, respectively, to prepare a solid BaTiO 3 of Example 12 in the same method and procedure as in Example 11.
마찬가지로, 비표면적(Sw)이 330m2/g인 아나타제형 TiO2분말을 준비하고, 합성 반응에서 생성된 BaTiO3의 Ba와 Ti의 몰비(Ba/Ti)가 1이 되도록, 이들 TiO2분말 및 Ba(OH)2·8H2O를 각각 202.01g 및 56.898g 칭량하여, 실시예 11과 동일한 방법·순서로 실시예 13의 고형물 형상 BaTiO3를 제조하였다.Similarly, anatase-type TiO 2 powders having a specific surface area (Sw) of 330 m 2 / g are prepared, and these TiO 2 powders and the molar ratio (Ba / Ti) of Ba and Ti of BaTiO 3 produced in the synthesis reaction are 1, and 202.01 g and 56.898 g of Ba (OH) 2 .8H 2 O were weighed, respectively, and a solid BaTiO 3 of Example 13 was prepared in the same manner and in the same manner as in Example 11.
또한, 비표면적(Sw)이 240m2/g인 아나타제형 TiO2분말을 준비하고, 합성 반응에서 생성된 BaTiO3의 Ba와 Ti의 몰비(Ba/Ti)가 1이 되도록, 이들 TiO2분말 및 Ba(OH)2·8H2O를 각각 75.721g 및 270.51g 칭량하여, 실시예 11와 동일한 방법·순서로 비교예 11의 고형물 형상 BaTiO3를 제조하였다.In addition, anatase-type TiO 2 powders having a specific surface area (Sw) of 240 m 2 / g were prepared, and these TiO 2 powders were formed such that the molar ratio (Ba / Ti) of Ba and Ti of BaTiO 3 produced in the synthesis reaction was 1; 75.721 g and 270.51 g of Ba (OH) 2 .8H 2 O were weighed, respectively, and a solid BaTiO 3 of Comparative Example 11 was prepared in the same manner and in the same manner as in Example 11.
다음으로, 실시예 11∼13 및 비교예 11의 BaTiO3에 대하여 XRD로 X선 회절을 실시하였다.Next, X-ray diffraction was performed by XRD on BaTiO 3 of Examples 11 to 13 and Comparative Example 11.
도 13은 X선 회절의 측정 결과를 나타내는 특정도로서, 횡축은 회절각 2θ(°), 종축은 강도(임의 단위)이다. 또한, 도면 중 파형도의 피크 위에 나타낸 △, ■, □는 이상의 생성을 나타내고 있고, △는 BaCO3, ■는 Ba2TiO4, □는 BaTi2O5를 각각 나타내고 있다. 예를 들면, 비교예 11에서는 회절각 2θ가 25°, 및 28°근방에서 2개의 뾰족한 피크가 생기고, 그 피크의 위쪽에 □가 기록되어 있는데, 이것은 해당 피크에서 BaTi2O5의 이상이 생성되어 있다는 것을 나타내고 있다. 마찬가지로 비교예 11에서는 회절각 2θ가 29°근방에서 뾰족한 피크가 생기고, 그 피크의 위쪽에 ■가 기록되어 있는데, 이것은 해당 피크에서 Ba2TiO4의 이상이 생성되어 있다는 것을 나타내고 있다.FIG. 13: is a specific figure which shows the measurement result of X-ray diffraction, a horizontal axis is a diffraction angle 2 (theta), and a vertical axis is intensity (arbitrary unit). Also, △, ■, shown above the peak of the waveform in the figure □ denotes a generation or more, △ is a BaCO 3, ■ is Ba 2 TiO 4, □ shows the BaTi 2 O 5, respectively. For example, in Comparative Example 11, two sharp peaks occur at the diffraction angle 2θ at 25 ° and 28 °, and □ is recorded at the upper part of the peak, which results in abnormality of BaTi 2 O 5 at the peak. It shows that it is. Similarly, in Comparative Example 11, a sharp peak occurs at the diffraction angle 2θ near 29 °, and? Is recorded above the peak, indicating that an abnormality of Ba 2 TiO 4 is generated at the peak.
도 13으로부터 알 수 있듯이, 비교예 11(비표면적(Sw)이 240m2/g)에서는 회절각 2θ가 20∼60°의 넓은 범위에서 BaCO3, BaTi2O5 및 Ba2 TiO4의 이상이 생기는 것에 비하여, 실시예 11∼13(비표면적(Sw)이 250∼330m2/g)에서는 BaCO3의 이상은 약간 확인되지만, BaTi2O5 및 Ba2TiO4의 생성은 확인되지 않았다. 따라서, 비표면적(Sw)이 적어도 250m2/g 이상인 TiO2분말을 사용할 필요가 있다는 것을 알 수 있었다.As can be seen from FIG. 13, in Comparative Example 11 (specific surface area (Sw) of 240 m 2 / g), abnormalities of BaCO 3 , BaTi 2 O 5, and Ba 2 TiO 4 were observed in a wide range of diffraction angle 2θ of 20 to 60 °. In contrast to the occurrence, in Examples 11 to 13 (specific surface area (Sw) of 250 to 330 m 2 / g), abnormality of BaCO 3 was slightly observed, but formation of BaTi 2 O 5 and Ba 2 TiO 4 was not confirmed. Therefore, it was found that it is necessary to use TiO 2 powder having a specific surface area (Sw) of at least 250 m 2 / g or more.
(제 4 실시예)(Example 4)
본 발명자들은 반응 공정에서 생성된 슬러리 형상 BaTiO3에 초음파를 조사하여 분말 성상을 조사하였다.The present inventors irradiated ultrasonically to the slurry-like BaTiO 3 produced | generated in the reaction process, and investigated the powder property.
즉, 우선 100℃의 증기를 순환시킨 가열 용기에 물 150㎖를 투입하여, 60℃의 가열수를 준비하였다. 이어서 합성 반응에서 생성된 BaTiO3의 Ba와 Ti의 몰비(Ba/Ti)가 1.003이 되도록, 비표면적(Sw)이 300m2/g인 아나타제형 TiO2 98.067g과 Ba(OH)2 185.318g을 상기 가열수에 투입하였다. 그리고 이것에 의해, Ba(OH)2는 발열을 동반하면서 합성 반응을 개시하여, 슬러리 형상 BaTiO3가 제조된다.That is, 150 ml of water was put into the heating container which circulated the steam of 100 degreeC, and 60 degreeC heating water was prepared first. Subsequently, 98.067 g of anatase-type TiO 2 having a specific surface area (Sw) of 300 m 2 / g and 185.318 g of Ba (OH) 2 were formed so that the molar ratio (Ba / Ti) of Ba and Ti of BaTiO 3 produced in the synthesis reaction was 1.003. Into the heated water. And by this, Ba (OH) 2 may initiate the synthetic reaction accompanied with heat generation, a slurry-like BaTiO 3 are prepared.
이어서, 자력교반기(Magnetic Stirrer)를 사용하여 상기 슬러리 형상 BaTiO3를 교반하는 한편, 초음파 조사 장치의 혼(horn)을 상기 슬러리 형상 용액에 침지하여, 주파수 16kHz의 초음파를 상기 슬러리 형상 BaTiO3에 조사하였다.Subsequently, the slurry-like BaTiO 3 was stirred using a magnetic stirrer, while a horn of an ultrasonic irradiation device was immersed in the slurry-like solution, and ultrasonic waves having a frequency of 16 kHz were irradiated to the slurry-like BaTiO 3 . It was.
이어서, 제 2 실시예와 거의 동일하게, 탁상형 샌드밀을 사용하여 슬러리를 제조한 후, 슬러리를 배출하여 200℃로 가열한 오븐 안으로 반송하고, 상기 오븐 안에서 수분을 증발 건조시켜서 고형물 형상 BaTiO3(200℃ 건조품)를 제조하였다.Subsequently, almost the same as in the second embodiment, after preparing a slurry using a table-type sand mill, the slurry was discharged and returned to an oven heated to 200 ° C., and water was evaporated to dryness in the oven to form a solid BaTiO 3. (200 degreeC dried product) was manufactured.
얻어진 BaTiO3분말 중의 Ba와 Ti의 몰비(Ba/Ti)를 XRF로 측정하였더니 0.9998이었다.The molar ratio (Ba / Ti) of Ba and Ti in the obtained BaTiO 3 powder was 0.9998 when measured by XRF.
다음으로, XRD로 X선 회절을 실시하여 이상 생성의 유무를 조사하였다.Next, X-ray diffraction was performed with XRD to check for the presence of abnormality generation.
도 14는 X선 회절의 측정 결과를 나타내는 특성도로서, 횡축은 회절각 2θ(°), 종축은 강도(임의 단위)이다.14 is a characteristic diagram showing a measurement result of X-ray diffraction, the horizontal axis is diffraction angle 2θ (°), and the vertical axis is intensity (arbitrary unit).
도 14로부터 알 수 있듯이, BaTiO3 중에는 Ba2TiO4 등의 이상이 생성되지 않았다. 따라서 하소 전의 단계에서 고순도의 고형물 형상 BaTiO3를 얻을 수 있다는 것이 확인되었다.As can be seen from FIG. 14, no abnormality such as Ba 2 TiO 4 was generated in BaTiO 3 . Therefore, it was confirmed that high purity solid BaTiO 3 can be obtained in the step before calcination.
이어서, 본 발명자들은 제 2 실시예와 마찬가지로, 상기 X선 회절의 결과에 기초하여 축비(c/a)를 산출하고, 200℃ 건조품인 고형물 형상 BaTiO3에 대하여 BET법으로 비표면적(Sw)을 측정하여, 상기 비표면적(Sw)으로부터 비표면적 구상당 직경(D)을 산출하였다.Next, the inventors calculate the axial ratio (c / a) on the basis of the result of the X-ray diffraction as in the second embodiment, and determine the specific surface area (Sw) by the BET method for the solid-state BaTiO 3 which is a 200 ° C dried product. By measuring, the specific surface area spherical diameter (D) was calculated from the specific surface area (Sw).
표 2는 그 측정 결과를 나타낸다.Table 2 shows the measurement results.
표 2에서 알 수 있듯이 초음파 조사를 거쳐 생성된 200℃ 건조품은, 비표면적(Sw)이 64.08m2/g이고 비표면적 구상당 직경(D)이 15.6nm으로 작으며, 초음파 조사를 하지 않은 제 2 실시예의 200℃ 건조품(표 1 참조)에 비하여, 보다 한층 미립화가 가능하고, 또한 축비(c/a)도 1.000으로 입방정계인 것이 확인되었다.As can be seen from Table 2, the 200 ° C dried product produced through ultrasonic irradiation has a specific surface area (Sw) of 64.08 m 2 / g and a specific surface area spherical diameter (D) of 15.6 nm. Compared with the 200 degreeC dry goods (refer Table 1) of Example 2, it was confirmed that atomization was possible more and the axial ratio (c / a) was also 1.000 and it was a cubic system.
(제 5 실시예)(Example 5)
제 2 실시예와 동일하게 하여 온도 200℃로 가열한 오븐에서 수분을 증발 건조시켜서 얻어진 BaTiO3를 용매로서의 이소프로필알콜과 함께, 볼밀에 투입하여 10시간 습식 분쇄 처리를 실시하고, BaTiO3를 이소프로필알콜 중에 분산시켰다. 그리고, 온도 200℃로 가열한 오븐에서 수분을 증발 건조시켜서 고형물 형상으로 한 후, 온도 900℃, 950℃, 1000℃에서 각각 2시간 소성 처리를 실시하여 BaTiO3분말(하소품)을 얻었다.BaTiO 3 obtained by evaporating and drying moisture in an oven heated to a temperature of 200 ° C in the same manner as in the second embodiment was added to a ball mill with isopropyl alcohol as a solvent, and wet grinding was performed for 10 hours, and BaTiO 3 waso-isolated. Dispersed in propyl alcohol. Then, the water was evaporated to dryness in an oven heated to a temperature of 200 ° C. to form a solid, and then calcined for 2 hours at temperatures of 900 ° C., 950 ° C. and 1000 ° C., respectively, to obtain BaTiO 3 powder (calcined product).
다음으로 본 발명자들은 200℃ 건조품(미하소품) 및 하소품에 대하여, 제 2 실시예와 마찬가지로 축비(c/a), 비표면적(Sw), 비표면적 구상당 직경(D)을 측정하였다.Next, the present inventors measured axial ratio (c / a), specific surface area (Sw), and specific surface area spherical diameter (D) about 200 degreeC dry goods (uncalcined goods) and calcined goods similarly to 2nd Example.
표 3은 그 결과를 나타낸다.Table 3 shows the results.
표 3에서 알 수 있듯이, 950℃ 이상에서 하소함으로써 분산 공정을 거치지 않은 제 2 실시예(표 1)와 비교하여, 비표면적(Sw)은 작아지지만 축비(c/a)는 향상되는 것을 알 수 있었다.As can be seen from Table 3, the specific surface area (Sw) is small but the axial ratio (c / a) is improved as compared with the second embodiment (Table 1) which is not subjected to the dispersion process by calcining at 950 ° C or higher. there was.
이상 상술한 바와 같이 본 발명에 따른 복합 산화물 분말의 제조 방법은, 일반식 ABO3로 표시되는 페로브스카이트 구조를 갖는 복합 산화물 분말을 제조하는 복합 산화물 분말의 제조 방법으로, 결정수를 함유한 A사이트 성분을 구성하는 원소의 수산화물을 가열하여 상기 A사이트 성분을 함유한 용해액을 생성하는 용해액 생성 공정과, 소정의 초미립자로 이루어지는 B사이트 성분을 구성하는 원소의 산화물 분말과 상기 용해액을 반응시켜서 반응 합성물을 생성하는 반응 공정을 포함하기 때문에, 양호한 결정성을 갖고 또한 미립의 복합 산화물을 저렴한 가격으로 얻을 수 있다.Above as a method of manufacturing composite oxide powder for producing a method of manufacturing composite oxide powder according to the present invention, composite oxide powder having a perovskite structure represented by a general formula ABO 3 as described above, containing water of crystallization A dissolution solution generation step of heating a hydroxide of an element constituting the A-site component to produce a dissolution solution containing the A-site component, an oxide powder of the element constituting the B-site component composed of predetermined ultrafine particles, and the dissolution solution Since it contains the reaction process which makes it react and produces | generates a reaction compound, a fine composite oxide can be obtained at low price with favorable crystallinity.
또한, 상기 수산화물을 수산화 바륨 8수화물로 하고, 상기 산화물 분말을 산화 티탄 분말로 함으로써, 저렴한 가격으로 상술한 원하는 BaTiO3를 얻을 수 있다.In addition, the above-mentioned desired BaTiO 3 can be obtained at low price by using the hydroxide as barium hydroxide octahydrate and the oxide powder as titanium oxide powder.
또한, A사이트 원소를 구성하는 원소의 수산화물 무수염과, 상기 수산화물이 결정수를 함유한 경우에 있어서의 상기 결정수와 동등한 수량을 혼합하여 A사이트 성분을 함유한 용해액을 생성하는 용해액 생성 공정과, 소정의 초미립자로 이루어지는 B사이트 성분을 구성하는 원소의 산화물 분말과 상기 용해액을 반응시켜서 반응 합성물을 생성하는 반응 공정을 포함하도록 하여도, 상기와 동일한 작용 효과를 얻을 수 있다. In addition, a solution for producing a solution containing A-site component is obtained by mixing a hydroxide anhydride of an element constituting the A-site element with a quantity equal to that of the crystallized water when the hydroxide contains crystal water. The same effect as above can be obtained even if it includes the process and the reaction process which produces | generates a reaction compound by making the said oxide solution react with the oxide powder of the element which comprises the B site component which consists of predetermined ultrafine particles.
이 경우에도 상기 수산화물을 수산화 바륨 무수염으로 하고, 상기 산화물 분말을 산화 티탄 분말로 함으로써, 상기와 동일하게 저렴한 가격으로 원하는 BaTiO3를 얻을 수 있다.Also in this case, by using the hydroxide as the barium hydroxide anhydrous salt and the oxide powder as the titanium oxide powder, desired BaTiO 3 can be obtained at the same low cost as described above.
또한, 상기 소정의 초미립자는 비표면적을 250m2/g 이상으로 함으로써, 이상이 적고 원하는 초미립이고 결정성이 우수한 복합 산화물을 제조할 수 있다.In addition, the predetermined ultrafine particles can produce a complex oxide having a specific surface area of 250 m 2 / g or more and less than the desired ultrafine particles with excellent crystallinity.
또한, 상기 A사이트 성분과 상기 B사이트 성분의 비(A/B)가 몰비로 0.990∼1.010이 되도록, 상기 수산화물 및 상기 산화물 분말의 칭량을 조정함으로써, 복합 산화물 안으로의 불순물의 혼입을 피한 고순도의 복합 산화물 분말을 제조할 수 있다.Further, by adjusting the weighing of the hydroxide and the oxide powder so that the ratio (A / B) of the A-site component and the B-site component is 0.990 to 1.010 in molar ratio, it is possible to avoid the incorporation of impurities into the complex oxide. Composite oxide powders can be prepared.
또한, 상기 반응 공정은 대기압 하에서 실행할 수 있기 때문에, 대규모의 특수 장치를 필요로 하지 않고, 원하는 복합 산화물 분말을 저렴한 가격으로 제조할 수 있다.In addition, since the reaction process can be carried out at atmospheric pressure, a desired complex oxide powder can be produced at a low price without requiring a large-scale special apparatus.
또한, 상기 반응 공정이 초음파를 조사하는 조사 공정을 포함함으로써, 하소 전의 단계에서 비표면적이 60∼100m2/g으로 이루어지는 보다 한층 미립화된 반응 합성물을 생성할 수 있다.In addition, since the reaction step includes an irradiation step of irradiating ultrasonic waves, it is possible to produce a further atomized reaction compound having a specific surface area of 60 to 100 m 2 / g in the step before calcination.
또한, 본 발명의 제조 방법이 상기 반응 합성물을 하소하여 상기 복합 산화물을 제조하는 하소 공정을 포함하기 때문에, 결정성이 우수한 입방정계 복합 산화물 분말로부터 하소에 의해 결정계가 전이하여 결정성이 우수한 정방정계 복합 산화물 분말을 제조할 수 있다. In addition, since the production method of the present invention includes a calcining step of calcining the reaction compound to produce the complex oxide, the crystal system is transformed by calcining from a cubic complex oxide powder having excellent crystallinity and a tetragonal crystal system having excellent crystallinity. Composite oxide powders can be prepared.
또한, 본 발명의 제조 방법은 상기 반응 합성물을 용매에 분산하는 분산 공정과, 상기 분산 공정에서 분산된 상기 반응 합성물을 하소하여 상기 복합 산화물을 제조하는 하소 공정을 포함함으로써, 하소함으로써 축비(c/a)를 보다 한층 향상시킬 수 있다.In addition, the production method of the present invention includes a dispersing step of dispersing the reaction compound in a solvent and a calcining step of calcining the reaction compound dispersed in the dispersing step to produce the complex oxide. a) can be further improved.
도 1은 본 발명에 따른 복합 산화물의 제조 방법의 한 실시형태를 나타내는 블럭 공정도.BRIEF DESCRIPTION OF THE DRAWINGS The block process diagram which shows one Embodiment of the manufacturing method of the complex oxide which concerns on this invention.
도 2는 본 발명의 BaTiO3의 합성 경로(1)를 나타내는 도면.2 shows a synthetic route 1 of BaTiO 3 of the present invention.
도 3은 본 발명의 BaTiO3의 합성 경로(2)를 나타내는 도면.3 shows a synthetic route 2 of BaTiO 3 of the present invention.
도 4는 BaTiO3의 합성 반응 과정에 있어서, 반응을 개시하고 나서 5분 후의 결정 상태를 나타내는 TEM사진.4 is a TEM photograph showing the crystal state 5 minutes after the start of the reaction in the course of the synthesis reaction of BaTiO 3 .
도 5는 BaTiO3의 합성 반응 과정에 있어서, 반응을 개시하고 나서 30분 후의 결정 상태를 나타내는 TEM사진.5 is a TEM photograph showing a crystal state 30 minutes after the start of the reaction in the course of the synthesis reaction of BaTiO 3 .
도 6은 BaTiO3의 합성 반응 과정에 있어서, 반응을 개시하고 나서 60분 후의 결정 상태를 나타내는 TEM사진.FIG. 6 is a TEM photograph showing the crystal state 60 minutes after the start of the reaction in the course of the synthesis reaction of BaTiO 3. FIG.
도 7은 BaTiO3의 미하소품(200℃ 건조품)의 SEM사진.7 is a SEM photograph of the uncalcined product (200 ° C. dried product) of BaTiO 3 .
도 8은 BaTiO3의 900℃ 하소품의 SEM사진.8 is a SEM photograph of a 900 ° C. calcined product of BaTiO 3 .
도 9는 BaTiO3의 950℃ 하소품의 SEM사진.9 is a SEM photograph of a 950 ° C. calcined product of BaTiO 3 .
도 10은 BaTiO3의 1000℃ 하소품의 SEM사진.10 is a SEM photograph of a 1000 ° C. calcined product of BaTiO 3 .
도 11은 제 2 실시예에 있어서의 X선 회절선도.Fig. 11 is an X-ray diffraction diagram in the second embodiment.
도 12는 본 발명의 실시예의 BaTiO3분말의 입자 직경과 축비(c/a)의 관계를 비교예과 함께 나타낸 특성도.12 is a characteristic view showing the relationship between the particle diameter and the axial ratio (c / a) of the BaTiO 3 powder of the embodiment of the present invention with a comparative example.
도 13은 제 3 실시예에 있어서의 X선 회절선도.Fig. 13 is an X-ray diffraction diagram in the third embodiment.
도 14는 제 4 실시예에 있어서의 X선 회절선도.Fig. 14 is an X-ray diffraction diagram in the fourth embodiment.
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| US20090135546A1 (en) * | 2007-11-27 | 2009-05-28 | Tsinghua University | Nano complex oxide doped dielectric ceramic material, preparation method thereof and multilayer ceramic capacitors made from the same |
| SI2358641T1 (en) | 2008-11-04 | 2014-10-30 | Sachtleben Pigments Oy | Process of preparing titanates |
| JP5184333B2 (en) * | 2008-12-25 | 2013-04-17 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Method for manufacturing dielectric ceramic material |
| JP5445412B2 (en) * | 2010-09-17 | 2014-03-19 | 株式会社村田製作所 | Method for producing composite oxide powder |
| JP5375838B2 (en) * | 2011-01-05 | 2013-12-25 | 株式会社村田製作所 | Method for producing perovskite complex oxide powder |
| JP5573729B2 (en) | 2011-02-25 | 2014-08-20 | 株式会社村田製作所 | Method for producing perovskite complex oxide |
| JP5920535B2 (en) | 2013-06-12 | 2016-05-18 | 株式会社村田製作所 | Method for producing barium titanate |
| TWI635048B (en) * | 2013-08-23 | 2018-09-11 | 堺化學工業股份有限公司 | Process for producing barium titanate poweder |
| TWI635067B (en) * | 2013-11-19 | 2018-09-11 | 堺化學工業股份有限公司 | Method for producing barium titanate poweder |
| CN106629826B (en) * | 2016-05-20 | 2018-06-19 | 北京纳米能源与***研究所 | A kind of two-dimensional structure nm-class barium titanate material and preparation method thereof |
| US11472716B2 (en) | 2016-06-14 | 2022-10-18 | Denka Company Limited | High-purity barium titanate powder, method for producing same, resin composition, and fingerprint sensor |
| CN106587994B (en) * | 2016-12-16 | 2019-09-27 | 哈尔滨工程大学 | A kind of low temperature cold sintering preparation method of barium titanate ferroelectric ceramics |
| CN111333105A (en) * | 2020-03-05 | 2020-06-26 | 西安理工大学 | Method for preparing cubic tetragonal barium titanate by using hydrothermal method |
| CN113788494A (en) * | 2021-10-27 | 2021-12-14 | 上海大学(浙江·嘉兴)新兴产业研究院 | Preparation method of barium dititanate |
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| FR1456030A (en) * | 1965-09-06 | 1966-05-20 | Thann Fab Prod Chem | Dry process for the production of titanium oxide and installations for the application of this process |
| US3472776A (en) * | 1965-09-15 | 1969-10-14 | Charlotte Chem Lab Inc | Electrically stabilized ferroelectric compositions of perovskite lattice structure (batio3 plus mn impurities) and method of making the same |
| JPS5939726A (en) | 1982-08-25 | 1984-03-05 | Sony Corp | Manufacture of fine barium titanate particle |
| JPS6131345A (en) | 1984-07-25 | 1986-02-13 | 堺化学工業株式会社 | Manufacture of composition |
| JP2557344B2 (en) | 1986-05-01 | 1996-11-27 | 三井石油化学工業株式会社 | Method for treating inorganic hydroxide precipitate |
| US4764493A (en) | 1986-06-16 | 1988-08-16 | Corning Glass Works | Method for the production of mono-size powders of barium titanate |
| GB2193713B (en) | 1986-07-14 | 1990-12-05 | Cabot Corp | Method of producing perovskite-type compounds. |
| JPH0341664Y2 (en) | 1987-08-07 | 1991-09-02 | ||
| DE3739853A1 (en) * | 1987-11-25 | 1989-06-08 | Philips Patentverwaltung | METHOD FOR PRODUCING BARIUM TITANATE IN POWDER FORM |
| JPH0239451A (en) | 1988-07-28 | 1990-02-08 | Nec Corp | Handling jig |
| US5445806A (en) * | 1989-08-21 | 1995-08-29 | Tayca Corporation | Process for preparing fine powder of perovskite-type compound |
| JPH0558631A (en) | 1991-09-06 | 1993-03-09 | Murata Mfg Co Ltd | Production of perovskite-type multiple oxide powder |
| JPH0648734A (en) | 1992-07-27 | 1994-02-22 | Teika Corp | Production of crystalline titanic acid based perovskite-type fine particle |
| JP2590742B2 (en) | 1994-07-19 | 1997-03-12 | 日本電気株式会社 | Online message arrival management processing unit and online message arrival management method |
| JPH08119633A (en) | 1994-10-25 | 1996-05-14 | Sony Corp | Production of fine barium titanate particles |
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2002
- 2002-12-06 JP JP2002355073A patent/JP4200427B2/en not_active Expired - Fee Related
- 2002-12-27 KR KR10-2002-0085002A patent/KR100497938B1/en active IP Right Grant
- 2002-12-27 CN CNB02151593XA patent/CN1184167C/en not_active Expired - Lifetime
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| US20040028601A1 (en) | 2004-02-12 |
| JP4200427B2 (en) | 2008-12-24 |
| CN1184167C (en) | 2005-01-12 |
| KR20030057449A (en) | 2003-07-04 |
| US7556792B2 (en) | 2009-07-07 |
| CN1428310A (en) | 2003-07-09 |
| JP2003252623A (en) | 2003-09-10 |
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